EP3599018A1 - Sol-gel-material, das die aldehyde und ketone adsorbiert, und sein herstellungsverfahren - Google Patents

Sol-gel-material, das die aldehyde und ketone adsorbiert, und sein herstellungsverfahren Download PDF

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Publication number
EP3599018A1
EP3599018A1 EP19154042.6A EP19154042A EP3599018A1 EP 3599018 A1 EP3599018 A1 EP 3599018A1 EP 19154042 A EP19154042 A EP 19154042A EP 3599018 A1 EP3599018 A1 EP 3599018A1
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European Patent Office
Prior art keywords
group
acid
sol
gel
dihydrazide
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EP19154042.6A
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English (en)
French (fr)
Inventor
Mickael GINEYS
Frederic HAMMEL
Denis Paccaud
Mathilde SIBEAUD
Marie-Pierre SOM
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SEB SA
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SEB SA
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Priority to EP19737741.9A priority Critical patent/EP3829762A1/de
Priority to CN201980043010.4A priority patent/CN112384297B/zh
Priority to PCT/EP2019/068512 priority patent/WO2020020639A1/fr
Priority to KR1020217005565A priority patent/KR20210036380A/ko
Priority to US17/252,889 priority patent/US20210178364A1/en
Publication of EP3599018A1 publication Critical patent/EP3599018A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A61L9/014—Deodorant compositions containing sorbent material, e.g. activated carbon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
    • A61L9/048—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating air treating gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28019—Spherical, ellipsoidal or cylindrical
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20—Method-related aspects
    • A61L2209/22—Treatment by sorption, e.g. absorption, adsorption, chemisorption, scrubbing, wet cleaning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/45—Gas separation or purification devices adapted for specific applications
    • B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings

Definitions

  • the invention relates to a sol-gel material adsorbing aldehydes and ketones, its preparation process, its uses and an air purification apparatus using this material.
  • Aldehydes are among the most abundant household chemical pollutants. Their sources are extremely numerous. They can in particular be related to an external production such as the photo-oxidation of methane. However, the main sources of emission of aldehydes are found inside dwellings and are very diverse: resins and adhesives used to make agglomerated wood, particle board and plywood, textile coverings, wallpapers, paints, leathers, urea-formaldehyde insulating foams used as thermal insulators by injection into walls and partitions.
  • Formaldehyde is also a preservative, disinfectant and dehydrating agent. For these reasons, it is abundantly used as a solvent in hospitals for the disinfection of surgical instruments but also in the funeral services industry where we practice thanatopraxia.
  • the material is generally porous, preferably microporous, more preferably nanoporous, with a large specific surface.
  • the probe molecule is generally deposited by impregnation on the material in order to facilitate surface phenomena in the porous structure of the material.
  • a porous material for the removal of aldehydes and more specifically formaldehyde which is a nanoporous matrix of metal oxides comprising at least one function reactive to aldehydes.
  • the probe molecules described are the enaminones and the corresponding 3-diketone / amine pairs, the imines and the hydrazines, or the salts derived from these compounds.
  • the object of the present invention is to solve all or part of the drawbacks mentioned above, in particular by proposing a method for preparing a porous adsorbent material having improved mechanical resistance and an absence of migration of the probe molecule in a tropical atmosphere. (for example at about 80% relative humidity), while advantageously having a reduced amount of probe molecule in the material.
  • the process for preparing a porous sol-gel material adsorbent according to the invention uses a sol-gel precursor of the alkoxysilane type.
  • this alkoxysilane-type sol-gel precursor is chosen from tetramethyl orthosilicate (TMOS), methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), methyltriethoxysilane (MTES), dimethyldimethoxysilane and their mixtures, preferably tetramethyl orthosilicate also called tetramethoxysilane.
  • the synthesis of the gel in step i) is advantageously carried out from tetramethoxysilane or from a mixture of tetramethoxysilane and at least one other organosilicate precursor chosen from phenyltrimethoxysilane, phenyltriethoxysilane, fluoroalkyltrimethoxysilane, fluoroalkyltriethoxysilane, chloroalkyltrimethoxysilane, chloroalkyltriethoxysilane, alkyltrimethoxysilane, alkyltriethoxysilane, aminopropyltriethoxysilane and their mixtures.
  • organosilicate precursor chosen from phenyltrimethoxysilane, phenyltriethoxysilane, fluoroalkyltrimethoxysilane, fluoroalkyltriethoxysilane, chloroalkyltrimethoxysilane, chloroalkyltrie
  • the synthesis of the gel in step i) is carried out from tetramethoxysilane or from a mixture of tetramethoxysilane and at least one other organosilicate precursor chosen from chloroalkyltrimethoxysilane, chloroalkyltriethoxysilane, aminopropyltriethoxysilane and their mixtures.
  • the synthesis of the gel in step i) is carried out using tetramethoxysilane or a mixture of tetramethoxysilane and at least one other organosilicate precursor chosen from chloropropyltrimethoxysilane, chloropropyltriethoxysilane, (C3-C10) alkyletrimethoxysilane, (C3-C10) alkyletriethoxysilane, aminopropyltriethoxysilane and their mixtures.
  • organosilicate precursor chosen from chloropropyltrimethoxysilane, chloropropyltriethoxysilane, (C3-C10) alkyletrimethoxysilane, (C3-C10) alkyletriethoxysilane, aminopropyltriethoxysilane and their mixtures.
  • the synthesis of the gel in step i) is carried out from tetramethoxysilane or from a mixture of tetramethoxysilane and at least one other organosilicate precursor chosen from propyltrimethoxysilane, propyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysane propyltrimethoxysilane, propyltriethoxysilane, aminopropyltriethoxysilane and mixtures thereof.
  • the synthesis of the gel in step i) is carried out using tetramethoxysilane or a mixture of tetramethoxysilane and at least one other organosilicate precursor chosen from chloropropyltrimethoxysilane and an aminopropyltriethoxysilane, more preferably still chosen from (3 -chloropropyl) trimethoxysilane (CITMOS), and (3-aminopropyl) triethoxysilane (APTES).
  • organosilicate precursor chosen from chloropropyltrimethoxysilane and an aminopropyltriethoxysilane, more preferably still chosen from (3 -chloropropyl) trimethoxysilane (CITMOS), and (3-aminopropyl) triethoxysilane (APTES).
  • step i) is carried out using tetramethoxysilane or a mixture of tetramethoxysilane and (3-chloropropyl) trimethoxysilane (CITMOS), or a mixture of tetramethoxysilane and (3-aminopropyl) triethoxysilane (APTES ).
  • CITMOS tetramethoxysilane or a mixture of tetramethoxysilane and (3-chloropropyl) trimethoxysilane
  • APTES a mixture of tetramethoxysilane and (3-aminopropyl) triethoxysilane
  • the process for the preparation of a porous sol-gel material adsorbent according to the invention uses a probe molecule of general formula (I) or a salt thereof.
  • (C1-C6) alkyl group
  • a saturated, linear or branched monovalent hydrocarbon chain comprising 1 to 6, preferably 1 to 4, carbon atoms.
  • (C3-C7) cycloalkyl group, it is necessary to understand, within the meaning of the present invention, a cyclic saturated hydrocarbon chain, comprising 3 to 7 cyclic carbon atoms.
  • a cyclic saturated hydrocarbon chain comprising 3 to 7 cyclic carbon atoms.
  • alkyl- (C3-C7) cycloalkyle should be understood, within the meaning of the present invention, a (C3-C7) cycloalkyl group as defined above, linked to the rest of the molecule via an (C1-C6) alkyl chain as defined above.
  • (C1-C16) alkyl group, it is necessary to understand, within the meaning of the present invention, a saturated, linear or branched monovalent hydrocarbon chain comprising 1 to 16, preferably 1 to 10, more preferably 1 to 8 atoms of carbon.
  • (C2-C16) alkenyl group
  • a monovalent hydrocarbon chain linear or branched, comprising at least one double bond and comprising 2 to 16 carbon atoms.
  • (C2-C16) alkynyl group
  • a monovalent hydrocarbon chain linear or branched, comprising at least one triple bond and comprising 2 to 16 carbon atoms.
  • (C1-C16) haloalkyl is meant, within the meaning of the present invention, a group (C1-C16) alkyl, as defined above, for which one or several hydrogen atoms have been replaced by a halogen atom as defined below. It may in particular be a CF3 group.
  • halogen atom is meant, in the sense of the present invention, fluorine, chlorine, bromine or iodine atoms.
  • aryl it is necessary to understand, within the meaning of the present invention, an aromatic hydrocarbon group, preferably comprising from 6 to 10 carbon atoms, and comprising a ring or several joined rings, such as for example a phenyl or naphthyl group.
  • aromatic hydrocarbon group preferably comprising from 6 to 10 carbon atoms, and comprising a ring or several joined rings, such as for example a phenyl or naphthyl group.
  • it is phenyl.
  • aryloxy group it is to be understood, within the meaning of the present invention, any aryl group as defined above, linked to the rest of the molecule via at least one oxygen atom. It may in particular be a phenyloxy group.
  • a monocyclic or polycyclic hydrocarbon, saturated, unsaturated or aromatic system comprising from 3 to 12 carbon atoms.
  • the polycyclic system comprises at least 2, in particular 2 or 3, contiguous or bridged cycles.
  • Each cycle of the monocyclic or polycyclic system advantageously comprises 3 to 8, in particular 4 to 7, in particular 5 or 6, carbon atoms.
  • aryl- (C1-C6) alkyl it is to be understood, within the meaning of the present invention, an aryl group as defined above, linked to the rest of the molecule via a chain (C1- C6) alkyl as defined above.
  • the process for the preparation of a porous sol-gel adsorbent material according to the invention uses a probe molecule of general formula (I) with R 1 , R 2 , R 3 , R 4 , R 5 , R 6 representing a hydrogen atom or a (C1-C6) alkyl group.
  • the process for preparing a porous sol-gel adsorbent material according to the invention uses a probe molecule of general formula (I) with Z representing a group (C1-C16) alkyl, preferably a group (C1 -C10) alkyl, or a C4, C6 or C8 alkyl group.
  • Z representing a group (C1-C16) alkyl, preferably a group (C1 -C10) alkyl, or a C4, C6 or C8 alkyl group.
  • the process for preparing a porous sol-gel adsorbent material according to the invention uses a probe molecule of general formula (I) with Z representing an aryl group or an aryl- (C1-C6) alkyl group.
  • the process for the preparation of a porous sol-gel adsorbent material according to the invention uses a probe molecule of general formula (I) with R 1 , R 2 , R 3 , R 4 , R 5 , R 6 representing a hydrogen atom or a (C1-C6) alkyl group, and with Z representing a (C1-C16) alkyl group, preferably a (C1-C10) alkyl group, or a C4, C6 or C8 alkyl group .
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 representing a hydrogen atom or a (C1-C6) alkyl group
  • Z representing a (C1-C16) alkyl group, preferably a (C1-C10) alkyl group, or a C4, C6 or C8 alkyl group.
  • the process for the preparation of a porous sol-gel adsorbent material according to the invention uses a probe molecule of general formula (I) with R 1 , R 2 , R 3 , R 4 , R 5 , R 6 representing a hydrogen atom or a (C1-C6) alkyl group, and with Z representing an aryl group or an aryl- (C1-C6) alkyl group.
  • the amine function of the probe molecule being a basic functional group, it can be in the form of salts. These salts include in particular the acid addition salts of the probe molecule.
  • the process for manufacturing the porous sol-gel adsorbent material according to the invention allows the probe molecule to be introduced during its preparation, that is to say in situ or One-pot (in English) and not by impregnation . It is advantageously a synthesis of the gel in step i) of the monotope synthesis type. That is to say that the synthesis is carried out in a single step with a sol-gel precursor of alkoxysilane type, for example tetramethoxysilane or a mixture of tetramethoxysilane and another organosilicate precursor, and the probe molecule (s) in the presence of inorganic and / or organic acid and water and optionally a polar organic solvent. This means that there is no impregnation of the probe molecule on the sol gel material but an intimate combination of the materials.
  • a sol-gel precursor of alkoxysilane type for example tetramethoxysilane or a mixture of tetramethoxysilane
  • the process for manufacturing the porous sol-gel adsorbent material according to the invention advantageously makes it possible to reduce the quantities of probe molecules compared to the processes by impregnation. The saturation of the specific surface by impregnation methods is thus avoided.
  • the process for preparing a porous sol-gel material adsorbent according to the invention is not a process by impregnation or immersion of the probe molecule.
  • the porous sol-gel adsorbent material according to the invention contains neither zeolite nor activated carbon.
  • the molar proportions of tetramethoxysilane / other organosilicate precursor can vary from 1 / 0.01 to 1 / 0.2, preferably 1/0, 01 to 1 / 0.04.
  • the aqueous composition used in step i) of the process according to the invention comprises a molar ratio of alkoxysilane precursor / probe molecule of from 1 / 0.1 to 1 / 0.001, preferably from 1 / 0.08 to 1 / 0.002, more preferably from 1 / 0.075 to 1 / 0.010, and in particular a ratio equal to 1 / 0.05 or 1 / 0.015.
  • the aqueous composition used in step i) of the process according to the invention comprises a molar ratio of TMOS / probe molecule of from 1 / 0.1 to 1 / 0.001, preferably from 1 / 0.08 to 1 / 0.002, more preferably from 1 / 0.075 to 1 / 0.010, and in particular a ratio equal to 1 / 0.05 or 1 / 0.015.
  • the synthesis of the gel in step i) is advantageously carried out in an aqueous medium in the presence of an inorganic and / or organic acid whose boiling point is greater than or equal to 100 ° C., preferably greater than or equal to 150 °. C, more preferably greater than or equal to 180 ° C.
  • the acid used according to the process of the invention is an acid exhibiting significant non-volatility.
  • the synthesis of the gel in step i) is advantageously carried out in an aqueous medium in the presence of an acid, preferably an acid having a pKA of at most 3.5, preferably at most 2.8.
  • the acid is an inorganic and / or organic acid chosen from sulfamic acid, phosphoric acid, paratoluene sulfonic acid, parahydroxybenzoic acid and their mixtures.
  • the acid used according to the process of the invention is a weakly hygroscopic acid.
  • Carrying out the synthesis in an acid medium makes it possible to obtain better coloring performance of the sol-gel matrix when the probe molecule, and in particular its amine group, reacts with aldehydes and / or ketones. Good performance is obtained when the pH of the aqueous medium is less than 3, preferably less than 2, preferably less than 2.5, more preferably less than 2.2 and even more preferably less than 1.8.
  • the synthesis of the gel in step i) is carried out in an aqueous medium.
  • the aqueous medium is water or a mixture of water and optionally a polar organic solvent.
  • the polar organic solvent can be a protic organic solvent, preferably a C1 to C6 aliphatic alcohol, more preferably methanol or ethanol. Those skilled in the art will easily be able to determine the necessary quantities of water and optionally of polar organic solvent as a function of the organosilicate precursor (s) used.
  • the method comprises a step iii) of drying the sol-gel material obtained after step ii). It is a step of evaporation of the water contained in the material. This can take place at room temperature for a prolonged period of a few days and under the action of heat or not.
  • this comprises a step iv) of baking the sol-gel material in addition to step iii) of drying.
  • This additional step of baking the sol-gel adsorbent material after it has been carried out can take place at a temperature of from 50 to 150 ° C, preferably from 60 to 80 ° C and in particular at 70 ° C.
  • Another object of the invention is the material capable of being obtained by the method according to the invention.
  • the expression material according to the invention is used without distinction to refer to the porous sol-gel material adsorbent according to the invention or to the material capable of being obtained by the method according to the invention.
  • the porous sol-gel adsorbent material according to the invention can be in the form of cylindrical granules with an L / D ratio> 1 in which L is the length of the granule and D is the diameter of the granule.
  • the subject of the invention is also the use of a material according to the invention, or of a material capable of being obtained by the method according to the invention for capturing aldehydes and / or ketones, in particular aldehydes chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, pentanal, hexanal, benzaldehyde and their mixture.
  • aldehydes chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, pentanal, hexanal, benzaldehyde and their mixture.
  • aldehyde any organic molecule having a terminal carbonyl function preferably chosen from formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, pentanal, hexanal and benzaldehyde.
  • the invention also relates to an air purification device using a material according to the invention or a material capable of being obtained by the method according to the invention.
  • the pollutant reacts with the probe molecule to form a third chemical entity of greater molecular weight which will remain trapped in the nanoporous network of the media.
  • filter comprising a specific adsorbent material. Unlike other adsorbents, this specific adsorbent material traps permanently by irreversible chemical transformation of the pollutant.
  • an aldehyde or a ketone comes into contact with the amino group (s) of the probe molecule, the carbonyl group reacts with the amine group to give an imine group. Generally, this first reaction does not produce coloring.
  • the porosity of the sol-gel material allows rapid diffusion of the aldehydes / ketones in the matrix in order to trap them and cause them to react with the amino groups of the probe molecule and obtain a change in saturation coloring.
  • the material according to the invention is generally porous, preferably microporous, more preferably nanoporous or mesoporous, with a large specific surface.
  • the nanoporous sol-gel materials according to the invention are in particular characterized in that they have a specific adsorption surface of 15 ⁇ 2 to 900 ⁇ 100 m 2 .g -1 , preferably 150 ⁇ 20 m 2 .g- 1 to 900 ⁇ 100 m 2 .g -1 .
  • the microporous sol-gel materials according to the invention also have a specific adsorption surface of 500 ⁇ 50 m 2 .g -1 to 900 ⁇ 100 m 2 .g -1 , preferably 650 ⁇ 70 m 2 .g -1 to 900 ⁇ 100 m 2 .g -1 and more preferably still from 750 ⁇ 70 m 2 .g -1 to 900 ⁇ 100 m 2 .g -1 .
  • the mesoporous sol-gel materials according to the invention advantageously have a specific adsorption surface of 15 ⁇ 2 to 400 ⁇ 40 m 2 .g -1 and more preferably still of 150 ⁇ 20 m 2 .g -1 to 300 ⁇ 50 m 2 .g -1 .
  • the specific surface and the distribution of pore sizes are determined by analysis of the adsorption-desorption isotherm with liquid nitrogen with the DFT (Density Functional Theory) model.
  • the material according to the invention makes it possible to eliminate harmful pollutants such as formaldehyde, a molecule that conventional adsorbent materials cannot or only slightly eliminate.
  • the specific adsorbent material according to the invention may comprise a nanoporous sol-gel matrix of metal oxides, said matrix containing at least one probe molecule carrying at least one reactive function which can react with an aldehyde function.
  • Example 1 TMOS matrix doped with dihydrazide of adipic acid and sulfamic acid (Formulation E1).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 4 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / diiprazide of adipic acid / sulfamic acid are equal to 1 / 16.5 / 0.052 / 0.054.
  • Example 2 TMOS matrix doped with dihydrazide of adipic acid and sulfamic acid (Formulation E2).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / adipic acid dihydrazide / sulfamic acid are equal to 1 / 16.5 / 0.017 / 0.018.
  • Example 3 TMOS matrix doped with dihydrazide of adipic acid and phosphoric acid (Formulation E3).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / diiprazide of adipic acid / phosphoric acid are equal to 1 / 16.5 / 0.052 / 0.054.
  • Example 4 TMOS / MTMS matrix doped with dihydrazide of adipic acid and sulfamic acid (Formulation E4).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / MTMS / adipic acid dihydrazide / sulfamic acid are equal to 1 / 16.5 / 0.3 / 0.052 / 0.054.
  • Example 5 TMOS matrix doped with dihydrazide adipic acid and paratoluene sulfonic acid (Formulation E5).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reagents are TMOS / H 2 O / dihydrazide of adipic acid / paratoluene sulfonic acid are equal to 1 / 16.5 / 0.026 / 0.027.
  • Example 6 TMOS matrix doped with dihydrazide of terephthalic acid and sulfamic acid (Formulation E6).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / terephthalic acid / sulfamic acid dihydrazide are equal to 1 / 16.5 / 0.013 / 0.027.
  • Example 7 TMOS matrix doped with sebacic acid and sulfamic acid dihydrazide (Formulation E7).
  • the dry granules obtained are translucent. These granules are annealed at 70 ° C for 24 hours.
  • the molar proportions of the reactants are TMOS / H 2 O / sebacic acid / sulfamic acid dihydrazide are equal to 1 / 16.5 / 0.013 / 0.027.
  • the materials to be tested were exposed to formaldehyde concentrations of the order of 400 ppbv at a flow rate of 4 l / min. These conditions were obtained using the ETHERA generation bench presented in Figure 1 .
  • Formaldehyde is generated in a permeation oven regulated in temperature and nitrogen flow.
  • the formaldehyde obtained at contents of the order of several ppmv is diluted by the flow of dry compressed air and another of moist compressed air (HR ⁇ 100%) in order to obtain an air flow calibrated at 400 ppbv formaldehyde and 50% humidity.
  • This gas flow is then separated into three and sent to the sampling flasks B1, B2 and B3.
  • On the lines leading to B2 and B3 are test cartridges containing the materials to be studied.
  • the polluted formaldehyde gas therefore crosses the cartridges before arriving in the balloons B2 and B3.
  • the average concentration upstream and downstream of the cartridges is determined and these concentrations are converted into mass of formaldehyde per minute which arrives upstream of the cartridges and which emerges downstream. The difference between these two values makes it possible to determine the mass of formaldehyde trapped per minute of exposure.

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EP19154042.6A 2018-07-27 2019-01-28 Sol-gel-material, das die aldehyde und ketone adsorbiert, und sein herstellungsverfahren Withdrawn EP3599018A1 (de)

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EP19737741.9A EP3829762A1 (de) 2018-07-27 2019-07-10 Sol-gel-material zur adsorption von aldehyden und ketonen und verfahren zur herstellung davon
CN201980043010.4A CN112384297B (zh) 2018-07-27 2019-07-10 吸附醛和酮的溶胶-凝胶材料及其制备方法
PCT/EP2019/068512 WO2020020639A1 (fr) 2018-07-27 2019-07-10 Materiau sol-gel adsorbant les aldehydes et les cetones, et son procede de preparation
KR1020217005565A KR20210036380A (ko) 2018-07-27 2019-07-10 알데히드 및 케톤 흡착성 졸-겔 물질 및 그의 제조 방법
US17/252,889 US20210178364A1 (en) 2018-07-27 2019-07-10 Sol-Gel Material Absorbing Aldehydes And Ketones, And The Process For Its Preparation

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EP3045224A1 (de) * 2013-09-13 2016-07-20 Toray Industries, Inc. Gasadsorptionsmittel, gasadsorptionsfolie und luftfilter
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CN112384297B (zh) 2024-02-23
EP3829762A1 (de) 2021-06-09
WO2020020639A1 (fr) 2020-01-30

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